Process for the single-bath dyeing of unmodified polyolefin fibers with metal-containing phthalocyanine

ABSTRACT

Process for the single-bath dyeing or printing of unmodified polyolefin fibers with metal-containing phthalocyanine dyestuffs, by reacting under high-temperature dyeing conditions on these textile materials aqueous liquors or printing pastes containing cationically modified phthalocyanine dyestuffs in the presence of a dispersion system on the basis of polyglycol ethers.

United States Patent [191 von der Eltz et al.

[73] Assignee: Hoechst Aktiengesellschaft,

Frankfurt am Main. Germain 221 Filed: Mar. 1. 1973 2] Appl. NQ; 336,902

[44] Published under the Trial Voluntary Protest Program on January 28. I975 as document no.

[30] Foreign Application Priority Data Mair. 7 [L172 Germain 2310879 [52] U.S. Cl 8/62; 8/l XA; 8/30;

[4 1 Nov. 11, 1975 8/lL8ll69; 8/17318/18t) Primary Emminur-Donzlld Le\' Arlumer, Agenl. ur Firm-( urtis. Morris 8; Sufford [57] ABSTRACT Process for the single-bath dyeing or printing of un modified pol \olefin fibers with metal-containing phthalocyunine dyestuffs. by reacting under hightemperuture dyeing conditions on these textile muteri als aqueous liquors or printing pastes cont-dining cutionicnlly modified phthzlloomnine d \estuffs in the presence of a dispersion system on the basis of pol glycol ethers.

[0 Claims. N0 Drawings PROCESS FOR THE SINGLE-BATH DYEING OF UNMODIFIED POLYOLEFIN FIBERS WITH METAL-CONTAINING PHTHALOCYANINE The present invention relates to a process for the single-bath dyeing of unmodified polyolefin fibers with metal-containing phthalocyanine dyestuffs.

It is known that unmodified polyolefin fibers, for example, polypropylene fibers, are, generally. difficult to dye by direct dyeing methods. Besides the immediate dyeing of the spinning mass in the melt with pigment dyestuffs, the dyeing of piece goods made of such fibers with aqueous suspensions of pigment dyestuffs and curable binding systems is described which form a correspondingly coloured film layer fast to washing on the fiber surface when being heated. Disperse dyes used for dyeing polyester fibers and other hydrophobic fibers, however, yield under comparable thermal conditions only very fair dyeings when being fixed the yield of which is unproportioned with respect to the amount of dyestuff used.

Various methods for the modification of the polyolefin material allow to improve the dye receptivity of the fiber considerably. For example, nitrogen-containing copolymers having a basic effect are introduced into the spinning melts of the fibrous ground substance of which the fibers consist and so anchored in the macromolecule. The fibers so modified then have affinity towards the anionic dyestuffs. Polypropylene can also be modified in such a manner that compounds of such metals which can form fast colour lakes with metallizable dyestuffs are incorporated into the mass or fiber. Thus, the fiber properties are influenced either by a metal-containing copolymer or by special aftertreatment operations of the finished, unmodified fibrous material before dyeing, for example, as described in German Auslegeschriften Nos. 1,297 577, 1,469 600 and l,6l9 601. But each of these processes for the modification of polyolefins requires additional operational expenditure which makes the fiber more expensive and sometimes inadvertantly affects the physical properties of the fiber, for example, by reducing its stability and elasticity or by increasing its inflammability.

It was, now, found, that unmodified polyolefin fibers, preferably polypropylene fibers, can be dyed or printed in a single-bath operation with metal-containing phthalocyanine dyestuffs when allowing aqueous liquors or printing pastes containing cationically modified phthalocyanine dyestuffs to act under high temperature dyeing conditions, on the textile materials mentioned in the presence ofa dispersion system on the basis of polyglycol ethers.

The present invention is based on the observation that the dyestuffs mentioned have a technically useful affinity towards the strongly hydrophobic, unmodified polyolefin fibers when they are present in a certain state of dispersion and are applied under adequate thermal conditions. Under these conditions, the dyeings or prints can be effected according to the process claimed using the exhaustion method, the pad-steaming method or a printing method together with steam fixation of the dyes. Taking into account a technical safety zone at a distance from the softening temperature of the fiber 150 l55C), the temperatures required are within the range of from l20 to 135C, preferably about l30C', the period of action is of 20 to 40 minutes, preferably of about 30 minutes, with the padsteaming and the print-steaming method, and of to 70 minutes, preferably about minutes, with the exhaustion method. It could not be expected that these conditions had been sufficient for the process of the invention to obtain a colour intensity which corresponded to the amount of dyestuff used.

The modified phthalocyanine dyestuffs to be used for carrying out the dyeings according to the new method contain as cationic radicals especially quaternary ammonium groups and are described in detail in literature. They are metal-containing phthalocyanine derivatives which contain 2 to 4 quaternary ammonium groups linked over methylene bridges to the benzene nuclei of the molecule. In these products the complex-bound metals to be considered are nickel, cobalt and, above all, copper. The quaternary nitrogen atom of the saltforming radical carries identical or different, lower alkylor hydroxyalkyl groups; the anionic constituent is represented by the hydroxyl ion or the anion of an inorganic or organic acid, especially the acetate. Compounds of this type are described, for example, in German Pat. No. l,220,065. Among the class of the phthalocyanine compounds which are water-soluble due to their salt-like substituents, the dyestuff of the formula COO CH CH -CH -0H is particularly suitable.

To carry out the process of the invention, it is essential that the dyestuff is suitably distributed in the liquid which allows a diffusion into and thus an absorption by the fiber, at best by means of an auxiliary mixture. This dispersion system essentially consists of a non-ionic auxiliary on the basis of alkylor alkylaryl-polyglycol ethers or oxethylated fatty acid polyglycol esters, preferably a reaction product of l mol of isotridecyl alcohol with 8 mols of ethylene oxide, which is combined in the exhaustion method with anionic protective colloids having a dispersing effect, preferably those ori the basis of lignin-sulfonic acid, and in the pad-steaming or print-steaming method with non-ionic protective colloids having a thickening effect, preferably a completely etherified locust bean flour.

When carrying out the process of the invention it was surprising that the simultaneous use of auxiliaries which split off acids under the action of heat (acidyielding agent), for example, of the type of the monohalogenoacetates of alkali metals, preferably sodium monochloroacetate, or of the type of the chromium(lIl)-acetato-sulfate of the formula at lower temperatures because of its cationic side chain. When the temperatures mentioned are reached, diffusion of the dycstuff from the surface to the interior of the fiber occurs. There is no doubt that the cationic group can be split off in this case. Such a reaction can be concluded from the efficiency of the acid-yielding agent (at least partially).

The following Examples illustrate the invention.

EXAMPLE 1 Flock material of unmodified polypropylene fibers was dyed in a dyeing apparatus under hightempera ture conditions, with a goods-to-liquor ratio of l 20, for 60 minutes with an aqueous liquid which contained, calculated on the weight of the dry material,

2 7c of a cationically modified phthalocyanine dyestuff of the formula C P CH -NCH CH C u c 2 3 3 O CH -CH -OH EXAMPLE 2 Piece-goods of unmodified polypropylene fibers were padded, with a liquor-pick-up of 70 by weight, with a liquid at room temperature which contained per liter of water 20 g of the dyestuff mentioned in Example I,

5 g of the reaction product of 1 mol ofisotridecyl alcohol with 8 mols of ethylene oxide and 10 g of a 2 aqueous solution ofa completely etherified locust bean flour.

After the application of the dyestuff the material so treated was dried, steamed in a pressure steamer at 130C for 30 minutes and then rinsed and finished in the usual manner.

A fast, brilliant turquoise dyeing was obtained.

When proceding by this method prints can also be effected on the material,

EXAMPLE 3 Dyeing was carried out in an analogous manner as described in Example I, using, however, concommittently 2 7c of sodium monochloroacetate as acid-yielding agent in the exhaustion bath. In this case, the yield of dyestuffis perceptibly better than that obtained by the prescription given in Example l.

EXAMPLE 4 Dyeing was carried out in an analogous manner as described in Example 2, using, however, concomittently,

20 g/l of chromium-(lll)-acetato-sulfate in the padding liquor.

In this case, the yield of dyestuff obtained is perceptibly higher than that obtained according to Example 2.

When proceding by this method prints can also be effected on the material.

We claim:

I. An exhaust process for the single-bath dyeing or printing of unmodified polypropylene fibers, with metal-containing phthalocyanine dyestuffs, which comprises treating said fibers under high temperature dyeing conditions with aqueous dispersions containing a. metal-containing phthalocyanine dyestuffs having 2 to 4 quaternary ammonium groups linked over methylene bridges to the benzene nuclei of the phthalocyanine molecule,

b. alkyl or alkylenyl-polyglycol ether or oxethylated fatty acid polyglycol ester, and

c. anionic protective colloids comprising ligninsulfonic acid.

2. A process as claimed in claim 1, wherein the dyestuffs are applied to the fibers for 50-7O minutes at a temperature ranging from to l35C, preferably about C.

3. A process as claimed in claim 1 wherein the said phthalocyanine dyestuffs have the following formula CuPc- CH CH -CH OH 4. A process as claimed in claim I, wherein the said dispersion contains a non-ionic auxiliary comprising the reaction product of one mol of iso-tridecyl alcohol with 8 mols of ethylene oxide in combination with anionic protective colloids based on lignin-sulfonic acid.

5. A process as claimed in claim 1, wherein additional substances are employed for improving the color yield of the dyeing liquors, said substances splitting off acid under the influence of heat.

6. A process as recited in claim 5, wherein as the said acid-yielding substance, monohaloacctates of alkali metals, preferably sodium monochloro-acetate, or chromium (lll)-acetate-sulfates of the formula H C COO I ca coo \80 ca coo 4 COO CH 3 a. metal-containing phthalocyanine dyestuffs having 2 to 4 quaternary ammonium groups linked over methylene bridges to the benzene nuclei of the phthalocyanine molecule,

b. alkyl or alkylenyl-polyglycol ether or oxethylated fatty acid polyglycol ester; and

c. non-ionic protective colloids having a thickening effect comprising etherified locust bean flour,

8. A process as recited in claim 7 wherein the dyestuffs are padded or printed on the fibers and these paddings or prints are then steamed, with or without intermediate drying, in a pressure steamer at 120 to 135C for 20 to 40 minutes.

9. A process as claimed in claim 7, wherein the said phthalocyanine dyestuffs have the following formula 3 H CH OH CuPc- CH prising a completely etherified locust bean flour. 

1. AN EXHAUST PROCESS FOR THE SINGLE-BATH DYEING OR PRINTING OF UNMODIFIED POLYPROPYLENE FIBERS, WITH METAL-CONTAINING PHTHALOCYANINE DYESTUFFS, WHICH COMPRISES TREATING SAID FIBERS UNDER HIGH TEMPERATURE DYEING CONDITIONS WITH AQUEOUS DISPERSIONS CONTAINING A. METAL-CONTAINING PHTHALOCYANINE DYESTUFFS HAVING 2 TO 4 QUATERNARY AMMONIUM GROUPS LINKED OVER METHYLENE BRIDGES TO THE BENZENE NUCLEI OF THE PHTHAOCYANINE MOLECULE, B. ALKYL OR ALKYLENYL-POLYGLYCOL ETHEROR OXETHYLATED FATTY ACID POLYGLYCOL ESTER, AND C. ANIONIC PROTECTIVE COLLOIDS COMPRISING LIGNIN-SULFONIC ACID
 2. A process as claimed in claim 1, wherein the dyestuffs are applied to the fibers for 50-70 minutes at a temperature ranging from 120* to 135*C, preferably about 130*C.
 3. A process as claimed in claim 1 wherein the said phthalocyanine dyestuffs have the following formula
 4. A process as claimed in claim 1, wherein the said dispersion contains a non-ionic auxiliary comprising the reaction product of one mol of iso-tridecyl alcohol with 8 mols of ethylene oxide in combination with anionic protective colloids based on lignin-sulfonic acid.
 5. A process as claimed in claim 1, wherein additional substances are employed for improving the color yield of the dyeing liquors, said substances splitting off acid under the influence of heat.
 6. A process as recited in claim 5, wherein as the said acid-yielding substance, monohaloacetates of alkali metals, preferably sodium monochloro-acetate, or chromium-(III)-acetate-sulfates of the formula
 7. A pad-steaming or print steaming process for the single-bath dyeing or printing of unmodified polypropylene fibers, with metal-containing phthalocyanine dyestuffs, which comprises treating said fibers under high temperature dyeing conditions after padding or printing with aqueous dispersions containing a. metal-containing phthalocyanine dyestuffs having 2 to 4 quaternarY ammonium groups linked over methylene bridges to the benzene nuclei of the phthalocyanine molecule, b. alkyl or alkylenyl-polyglycol ether or oxethylated fatty acid polyglycol ester; and c. non-ionic protective colloids having a thickening effect comprising etherified locust bean flour.
 8. A process as recited in claim 7 wherein the dyestuffs are padded or printed on the fibers and these paddings or prints are then steamed, with or without intermediate drying, in a pressure steamer at 120* to 135*C for 20 to 40 minutes.
 9. A process as claimed in claim 7, wherein the said phthalocyanine dyestuffs have the following formula
 10. A process as rectied in claim 7, wherein said dispersion contains a non-ionic auxiliary based on the reaction product of one mol of iso-tridecyl alcohol with 8 mols of ethylene oxide in combination with non-ionic protective colloids having a thickening effect and comprising a completely etherified locust bean flour. 